Explosive



Patented Uct. 31, 1939 PATENT OFFICE EXPLOSIVE Edward B. W. Kerone andClayton 0. Carroll, Alton, IlL, assignors to Western Cartridge Company,East Alton, Ill.,

ware

No Drawing.

9 Claims.

This invention relates generally to explosives and particularly (tonitroso derivatives of resorcinol and the compounds thereof.

In the explosive compositions, such as those employed in the primingmixtures of ammunition, the ingredients must be selected with referencenot only to the explosive activity in the office or function which theingredient is to fulfill upon detonation, but care must also be taken toselect ingredients which are compatible with each other and which arestable under adverse atmospheric conditions. In some cases the severeatmospheric conditions may be artificial, but, where there is liabilitythat the ammunition may be subjected to them, it obviously must becapable of withstanding the severity and adversity of such conditions.

Heretofore considerable difflculty has been countered with primingmixtures insofar as maintenance of stability under adverse storageconditions is concerned. The usual priming mixture is composed of anumber of ingredients which fall, generally, into three classes, to-wit:initiators, oxidizers, and fuels and in some cases abrasives. With sucha mixture it is apparent that under certain conditions of temperature,moisture and the like, the respective ingredients are not only liabletodecompose of themselves, but reactions are liable to beset up amongthe respective ingredients resulting in deterioration of the primerwithconsequent unreliability of the ammunition.

The object of the present invention,'generally stated, is to provide anexplosive compound having a high order of stability under a variety ofconditions.

Another object of the present invention is to provide a fuel ingredientfor an ammunition priming mixture which is not only stable but iscompatible with the other ingredients of the priming mixture under avariety of conditions.

A more specific object of the invention is to provide anitrosoresorcinol compound capable of use as the fuel ingredient in apriming mixture for ammunition.

A further object of the present invention is to provide a process ofmaking nitrosoresorcinol compounds of an explosive character.

Other objects will become apparent to those skilled in the art when thefollowing description is understood.

In accordance with the present invention, compounds of nitrosoderivatives of resorcinol a provided and employed as ingredients ofexplosive compositions, such for instance as in the priming charge ofammunition and in other detonating Application October 12, 1936, SerialNo. 105,289

cyanate.

dinitrosoresorcinol may be used, the silver salt, for

instance, being somewhat less sensitive than the lead salt, and likewisethe eadmium andcopper a corporation of Delacharges. The'heavy metalsalts of the polynitrosoresorcinols particularly exhibit characteristosuch specific characteristicsas sensitivity and fiash point, the entiregroup of explosive nitrosoresorcinol compounds is characterized by ahigh order of stability even under extremely -severe and adverseconditions. On account of the relative ease and economy of theirmanufacture, compounds of dinitrosoresorcinol particularly commendthemselves for use. For instance, the lead salts of dinitrosoresorcinolprepared in any suitable manner may be used with particular advantage asthe fuel ingredients in an ammunition priming mixture. vIn addition tofulfilling the office and function of the ordinary fuel ingredient insuch a priming mixture, the lead salts of dinitrosoresorcinol aresomewhat sensitive to friction and impact and hence their presencecontributes .to the sensitivity of the priming composition, and,

in fact, smaller quantities of the initiating ingredient may be employedthan with other known fuels, such as antimony sulphide or lead thio-Likewise other heavy metal salts of salts.

Such salts of dinitrosoresorcinol may be pre-= pared fromdinitrosoresorcinol which latter may have been produced by any suitableprocess such, for instance, as that described by Orndorfl andi Nicholsin the Journal of the American Chemical Society, v0.1 45, page 1536(1923). The salts of dinitrosoresorcinol may be obtained by reactionwith the desired base in the usual manner for obtaining salts. The watersoluble salts of dinitrosoresorcinol may be readily made by treating agiven amount of dinitrosoresorcinol with an equivalent amount of a metalhydroxide or carbonate in aqueous solution and then evaporating thewater. Water insoluble salts of dinitrosoresorcinol can also be formedby this method provided the hydroxide or carbonate of the desired metalis itself soluble in water. In case, however, the hydroxide or carbonateof the metal desired is insoluble in water, as is the case with lead, adouble decomposition reaction between two salts 'is resorted toas, forinstance, by first making an alkali salt of dinitrosoresorcinol. Thisalkali salt maythen be reacted in the presence of a soluble lead saltsuch, for instance, as lead acetate orni- 'itate to settle, theSupernatant spherica trate with the result that leaddinitrosoresorcinate is precipitated while the other products of thereaction remain in solution.

Lead salts may be obtained in either an amorphous or granular form, theexplosive properties of each formbeing substantially the same, but,because of the greater convenience in handling the material, thegranular form is the more advantageous to use when the conventionalloading and mixing machinery is to be employed in the preparation andcharging of primer compositions. Moreover, the lead salts may beobtained as either the normal or the basic salt or in the form of amixture of the normal and the basic salts as will be more particularlydescribed hereinafter.

As one illustrative embodiment of the present invention, normal leaddinitrosoresorcinate may be obtained by treatment of dinitrosoresorcinolas follows: 60 grams of 2,4 dinitrosoresorcinol monohydrate aresuspended in 500 cc. of water and a solution of 28.5 grams of sodiumhydroxide in 100 cc. of water is added with stirring. This reacts toproduce a solution of sodium dinitrosoresorcinate. 15 cc. of thissolution are added to a solution of 132 grams of lead acetate and gramsof glacial acetic acid in 2,000 cc. of water heated to a temperature of80 C. The lead salt of the dinitrosoresorcinol immediately appears as abrown amorphous precipitate, but, upon vigorous agitation of the bathfor about five minutes, the amorphous precipitate is converted intoblack granules which are substantially spherical in shape. umdinitrosoresorcinate solution is then gradually added to the bath whilevigorous agitation thereof continues and the temperature maintained atabout 80 C. Substantially forty-five minutes may be consumed incompleting the mixture of the two solutions and agitation should proceedfor a short time as, for instance, five minutes after the two solutionshave been completely mixed, the mixture may then be permitted to standfor a time sufiicient to permit the granules of lead salt ofdinitrosoresorcinol washed with water and dried at a suitabletemperature, such for instance as C. The product of this reaction hasbeen identified as normal lead dinitrosoresorcinate having the followingformula:

. NO From the procedure above described, a yield of approximately 112grams of the blaclrspherifour hours in water, the flash point of 274 C.

was retained. When touched with a matchfiame, the salt defiagratesrapidly leaving an amorphous carbonaceous deposit. On analysis, the saltwas found to contain 55.53% lead, in close agree- The remainder of thesodirecipment with 55.52%, the theoretical lead content corresponding tothe formula given above.

As a further illustrative embodiment basic lead nitrosoresorcinate maybe prepared as follows:

A solution containing 25 grams of 2,4 dinitrosoresorcinol monohydrate,21.5 grams of sodium hydroxide, and 1000 cc. of water is gradually addedover a period of 50 minutes to a solution of 100 grams of lead nitratein 500 cc. of water, which is maintained at 80 C. and well agitated.After standing one-half hour, the product is obtained as a light brownprecipitate consisting of agglomerated amorphous particles. Theresultant product may be washed and dried as with the previous example.

The product has been determined to be basic lead dinitrosoresorcinatehaving the following formula:

Analysis shows the lead content of the product to be 67.09% insubstantial agreement with the theoretical value of 67.29% based uponthe formula.

The material has a flash point of 242 C. but is somewhat less sensitiveto impact than the normal lead salt of dinitrosoresorcinate described inthe previous embodiment. When touched with a match flame the substance,however, defiagrates more violently than the normal salt and thecarbonaceous residue is spread over a wider area.

In the apparatus employed for determining the flash points of thematerials as hereinbefore stated, the flash points of other knownexplosive materials are indicated as follows:

Degrees Centigrade As a further example of an illustrative. process inwhich the resultant product is composed of.

both the normal and basic salts of lead dinitrosoresorcinate thefollowing procedure may be carried out.

A solution containing 25 grams of 2,4 dinitrosoresorcinol monohydrate,21.5 grams of sodium hydroxide, and 1000 cc. of water, is graduallyadded over a period of 50 minutes to a solution containing 100 grams oflead acetate, 8 grams of glacial acetic acid, and 750 cc. of water,maintained at 80 C. and Well agitated. Until after' about one-third ofthe first solution has been added, the precipitate consists of the blackspherical granules characteristic of the normal salt. Following this,the color of the precipitate changes to the brown color of the basicsalt. After all the solution has been added, 8 grams of glacial aceticacid are added to the suspension in order .to complete the agglomerationof the particles, the addition causing a darkening of the precipitatewhich is probably due to the superficial conversion of basic to normalsalt. The precipitate is then thoroughly washed with water and dried.

From the last described procedure, using the proportions of ingredientsspecified, a product consisting of approximately one-third normal leaddinitrosoresorcinate and two-thirds basic dinitrosoresorcinate may beobtained. This coarseness of the precipitate may be increased by raisingthe temperature, increasing the time, and supplying more vigorousagitation during the precipitation.

As hereinbefore pointed out, the explosive compounds ofnitrosoresorcinol particularly commend themselves for' use in explosivecompositions on account of the higher order of stability exhibited bythese materials even under severe and adverse conditions of storage andtreatment. Consequently priming compositions and other explosivemixtures which are formulated with such nitrosoresorcinol compounds as,for instance, the lead salts of polynitrosoresorcinols are particularlyadvantageous insofar as the stability of the compound is concerned, itbeingobserved in this connection that instability of priming mixtureshas heretofore been frequently attributed to instability of fuelingredients therein.

As illustrating/the application of such explosive compounds ofnitrosoresorcinolin priming compositions, several illustrativeembodiments are set forth in the following, tables, it being observedthat each table sets forth a range of percentages for'each ingredient aswell as a specific example in each instance, the figures representingpercentages by weight:

Range Specific 1. Primer for shot shells: Percent Percent Mercuryfulminate 30-40 40 Lead salt of dinltroso resorcinol 3-15 5 Antimonysulfide 12-25 18 Barium nitrate 32 Lead dioxide -10 p 2. Rim-fireprimers:

a. Normal lead styphnate 35-50 40 Lead salt of dinitrosoresorcinol 3-156 Guanylmtrosaminoguanyl tetrazenel-8 4 Barium nitrate. 29 Ground glass10-30 Gum arable 1-2 1 b. Mercury fulminate 35-45 40 Lead salt ofdinitrosoresorcinol 5-15 11 Barium nitrate 15-35 22 Lead chromate 5-1511 15-40 30 Gnanylnitrosamincguanyl tetraz ene 1-5 3 Barium nitrate -5540. 5 Ground glass 5-20 10 Ester gum 1-4 2. 6

In any of the mixtures above referred to, either 0 the normal or thebasic lead salt of dinitrosoresorcinol, as described hereinbefore, ormixtures 'not to be understood that the present invention,

or its application to priming mixtures, is limited t0 the examples setforth in the foregoing tables. On the contrary, it is to be distinctlyunderstood that the compounds or combinations of compounds having arecognized function in priming mixtures may be substituted and replacedby other known compounds or combinations thereof having the samefunctions, adjustment being made when necessary in the proportions-ofthe ingredients. While in eachof the foregoing examples a lead salt ofdinitrosoresorcinal is included as the fuel ingredient in the primingmixtures, it is to be understood that dinitrosoresorcinol compounds maybe used either alone or in combination with other known and commonlyemployed fuels, such, for instance, as antimony sulfide, leadthiocyanate, calcium silicide and the like.

- While the invention has been .described with particular reference toexplosive compositions and particularly in connection with priming anddetonating compositions, and while the nitrosoresorcinol compounds ofthe present invention are particularly useful and advantageous in theexplosive field, it is not to be understood that the invention islimited thereto. On the contrary the present invention is to beunderstood as contemplating, generally, the novel compounds which havebeen disclosed herein regardless of the use I fore, that suchmodifications and the use of such combinations and subcombinations offeatures of claimed is: 1. An explosive comprising a salt of anitrosoresorcinol. 1

2. An explosive comprising a heavy of a nitrosoresorcinol.

metal salt 3. A priming composition containing a lead salt ofdinitrosoresorcinol.

4. A priming composition containing normal lead dinitrosoresorcinate.

5. A priming composition containing basic lead dinitrosoresorcinate.

6. A priming composition containing a mix-.- ture of normal and basiclead dinitrosoresorcinate. I

'7. A manufacture comprising spherical granules of a leadnitrosoresorcinate.

8. A priming composition comprising, an initiating ingredient, a leadsalt of dinitrosoresorcinol, and an oxidizing agent. v

9. An explosive comprising 2, 4 lead dinitrosoresorcinate.

EDWARD B. W. ICERONE. CLAYTON C. CARROLL.

